Procatalyst Composition with Alkoxypropyl Ester Internal Electron Donor and Polymer from Same

ABSTRACT

Disclosed herein are catalyst compositions and polymers, i.e., propylene-based polymers, produced therefrom. The present catalyst compositions include an internal electron donor with an alkoxypropyl ester. The present catalyst compositions improve catalyst selectivity. Propylene-based polymer produced from the present catalyst composition has a melt flow rate greater than 4 g/10 min.

BACKGROUND

The present disclosure provides a process for enhancing procatalyst andcatalyst properties. The present disclosure provides formant polymersproduced by these procatalysts/catalysts.

Worldwide demand for olefin-based polymers continues to grow asapplications for these polymers become more diverse and moresophisticated. Known are Ziegler-Natta catalyst compositions for theproduction of olefin-based polymers and propylene-based polymers inparticular. Ziegler-Natta catalyst compositions typically include aprocatalyst containing a transition metal halide (i.e., titanium,chromium, vanadium), a cocatalyst such as an organoaluminum compound,and optionally an external electron donor. Many conventionalZiegler-Natta catalyst compositions include a magnesiumchloride-supported titanium chloride procatalyst with a phthalate-basedinternal electron donor.

The health concerns from phthalate exposure are driving the art to findphthalate substitutes. Known are catalyst compositions containing analkoxyalkyl ester (AE) as an internal electron donor for the productionof propylene-based polymers. However, conventional AE-containingcatalysts are currently not viable because their catalyst activityand/or selectivity are too low for commercial application. Desirablewould be Ziegler-Natta procatalyst compositions containing analkoxyalkyl ester internal electron donor with sufficient catalystactivity/selectivity for the commercial (i.e., large-scale) productionof olefin-based polymers.

SUMMARY

The present disclosure provides a process for producing a Ziegler-Nattaprocatalyst composition containing an alkoxypropyl ester as an internalelectron donor. The Applicant has discovered that a procatalystcomposition containing alkoxypropyl ester of aliphatic acid (includingalkoxypropyl ester containing small/no substituents) as internalelectron donor which is made using a benzoate-containing magnesiumchloride precursor surprisingly improves catalyst selectivity comparedto conventional AE-containing catalysts.

The present disclosure provides a catalyst composition. In anembodiment, a catalyst composition is provided and includes aprocatalyst composition comprising a combination of a magnesium moiety,a titanium moiety, and greater than 6.5 wt % of an alkoxypropyl ester.The catalyst composition also includes a cocatalyst and an externalelectron donor.

The present disclosure provides a process. In an embodiment, a processfor producing a procatalyst composition is provided and includescontacting a procatalyst precursor with a halogenating agent in thepresence of an alkoxypropyl ester. The procatalyst precursor includes abenzoate-containing magnesium chloride. The process further includesforming a procatalyst composition comprising a magnesium moiety, atitanium moiety, and an internal electron donor comprising thealkoxypropyl ester.

The present disclosure provides another process. In an embodiment, apolymerization process is provided and includes contacting, underpolymerization conditions, propylene and optionally one or morecomonomers with a catalyst composition. The catalyst compositionincludes a procatalyst composition containing greater than 6.5 wt % ofan alkoxypropyl ester, a cocatalyst, and an external electron donor. Theprocess further includes forming a propylene-based polymer.

The present disclosure provides a composition. In an embodiment, apolymeric composition is provided and includes a propylene-based polymercomprising an alkoxypropyl ester and having a melt flow rate greaterthan 4 g/10 min.

An advantage of the present disclosure is the provision of an improvedprocatalyst/catalyst composition.

An advantage of the present disclosure is the provision of aprocatalyst/catalyst composition with improved selectivity for thepolymerization of olefin-based polymers.

An advantage of the present disclosure is a phthalate-freeprocatalyst/catalyst composition.

An advantage of the present disclosure is the provision of aphthalate-free catalyst composition and a phthalate-free olefin-basedpolymer produced therefrom.

An advantage of the present disclosure is the provision of an improvedprocatalyst/catalyst composition for production of olefin-based polymerswith reduced residual metal and halide contents.

DETAILED DESCRIPTION

The present disclosure provides a procatalyst composition having analkoxypropyl ester as an internal electron donor. The alkoxypropyl esterimproves catalyst selectivity.

In an embodiment, a catalyst composition is provided. The catalystcomposition includes a procatalyst composition, a cocatalyst, and anexternal electron donor. The procatalyst composition is a combination ofa magnesium moiety, a titanium moiety, and an alkoxypropyl ester. Theprocatalyst composition contains greater than 6.5 wt % of thealkoxypropyl ester based on the total weight of the procatalystcomposition.

Procatalyst Precursor

The procatalyst composition is formed by multiple contacts (two, three,or more) between a procatalyst precursor and a halogenating agent in thepresence of an alkoxypropyl ester (internal electron donor). Theprocatalyst precursor contains magnesium and may be a magnesium moietycompound (MagMo), a mixed magnesium titanium compound (MagTi), or abenzoate-containing magnesium chloride compound (BenMag). In anembodiment, the procatalyst precursor is a magnesium moiety (“MagMo”)precursor. The “MagMo precursor” contains magnesium as the sole metalcomponent. The MagMo precursor includes a magnesium moiety. Nonlimitingexamples of suitable magnesium moieties include anhydrous magnesiumchloride and/or its alcohol adduct, magnesium alkoxide or aryloxide,mixed magnesium alkoxy halide, and/or carbonated magnesium dialkoxide oraryloxide. In one embodiment, the MagMo precursor is a magnesium di(C₁₋₄)alkoxide. In a further embodiment, the MagMo precursor isdiethoxymagnesium.

In an embodiment, the procatalyst precursor is a mixedmagnesium/titanium compound (“MagTi”). The “MagTi precursor” has theformula Mg_(d)Ti(OR^(e))_(f)X_(g) wherein R^(e) is an aliphatic oraromatic hydrocarbon radical having 1 to 14 carbon atoms or COR′ whereinR′ is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbonatoms; each OR^(e) group is the same or different; X is independentlychlorine, bromine or iodine, preferably chlorine; d is 0.5 to 56, or 2to 4; f is 2 to 116 or 5 to 15; and g is 0.5 to 116, or 1 to 3. TheMagTi precursor is prepared by controlled precipitation through removalof an alcohol from the precursor reaction medium used in theirpreparation. In an embodiment, a reaction medium comprises a mixture ofan aromatic liquid, such as a chlorinated aromatic compound, orchlorobenzene, with an alkanol, especially ethanol. Suitablehalogenating agents include titanium tetrabromide, titaniumtetrachloride or titanium trichloride, especially titaniumtetrachloride. Removal of the alkanol from the solution used in thehalogenation, results in precipitation of the solid precursor, havingdesirable morphology and surface area. In a further embodiment, theresulting procatalyst precursor is a plurality of particles that areessentially uniform in particle size.

In an embodiment, the procatalyst precursor is a benzoate-containingmagnesium chloride material. As used herein, a “benzoate-containingmagnesium chloride” (“BenMag”) can be a procatalyst (i.e., a halogenatedprocatalyst precursor) containing a benzoate internal electron donor.The BenMag material may also include a titanium moiety, such as atitanium halide. The benzoate internal donor is labile and can bereplaced by other electron donors during procatalyst and/or catalystsynthesis. Nonlimiting examples of suitable benzoate groups includeethyl benzoate, methyl benzoate, ethyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-ethoxybenzoate, ethyl p-chlorobenzoate. In oneembodiment, the benzoate group is ethyl benzoate. Nonlimiting examplesof suitable BenMag procatalyst precursors include procatalysts of thetrade names SHAC™ 103 and SHAC™ 310 available from The Dow ChemicalCompany, Midland, Mich. In an embodiment, the BenMag procatalystprecursor may be a product of halogenation of any procatalyst precursor(i.e., a MagMo precursor or a MagTi precursor) in the presence of abenzoate compound.

Procatalyst Composition

The present disclosure provides a process. In an embodiment, a processfor producing a procatalyst composition is provided and includescontacting a procatalyst precursor with an alkoxypropyl ester and ahalogenating agent. The procatalyst precursor includes abenzoate-containing magnesium chloride (a BenMag procatalyst precursor).The process includes forming a procatalyst composition comprising amagnesium moiety, a titanium moiety, and an internal electron donorcomprising the alkoxypropyl ester.

The procatalyst precursor is contacted two, three, or more times with ahalogenating agent in the presence of an alkoxypropyl ester to form theprocatalyst composition. The alkoxypropyl ester is an internal electrondonor. As used herein, an “internal electron donor” (or “IED”) is acompound added or otherwise formed during formation of the procatalystcomposition that donates at least one pair of electrons to one or moremetals present in the resultant procatalyst composition. Not wishing tobe bound by any particular theory, it is believed that duringhalogenation (and titanation) the internal electron donor (1) regulatesthe formation of active sites and thereby enhances catalyststereoselectivity, (2) regulates the position of titanium on themagnesium-based support, (3) facilitates conversion of the magnesium andtitanium moieties into respective halides and (4) regulates thecrystallite size of the magnesium halide support during conversion.Thus, provision of the internal electron donor yields a procatalystcomposition with enhanced stereoselectivity. The internal electron donoris one, two, or more alkoxypropyl ester(s).

The term “contacting,” or “contact,” or “contact step” in the context ofprocatalyst synthesis, is the chemical reaction that occurs in areaction mixture (optionally heated) containing a procatalystprecursor/intermediate, a halogenating agent (with optional titanatingagent), an alkoxypropyl ester, and a solvent. The reaction product of a“contact step” is a procatalyst composition (or a procatalystintermediate) that is a combination of a magnesium moiety, a titaniummoiety, complexed with the alkoxypropyl ester (internal electron donor).

Halogenation (or halogenating) occurs by way of a halogenating agent. A“halogenating agent,” as used herein, is a compound that converts theprocatalyst precursor (or procatalyst intermediate) into a halide form.A “titanating agent,” as used herein, is a compound that provides thecatalytically active titanium species. Halogenation and titanationconvert the magnesium moiety present in the procatalyst precursor into amagnesium halide support upon which the titanium moiety (such as atitanium halide) is deposited.

In an embodiment, the halogenating agent is a titanium halide having theformula Ti(OR^(e))_(f)X_(h) wherein R^(e) and X are defined as above, fis an integer from 0 to 3; h is an integer from 1 to 4; and f+h is 4. Inthis way, the titanium halide is simultaneously the halogenating agentand the titanating agent. In a further embodiment, the titanium halideis TiCl₄ and halogenation occurs by way of chlorination of theprocatalyst precursor with the TiCl₄. The chlorination (and titanation)is conducted in the presence of a chlorinated or a non-chlorinatedaromatic or aliphatic liquid, such as dichlorobenzene, o-chlorotoluene,chlorobenzene, benzene, toluene, xylene, octane, or1,1,2-trichloroethane. In yet another embodiment, the halogenation andthe titanation are conducted by use of a mixture of halogenating agentand chlorinated aromatic liquid comprising from 40 to 60 volume percenthalogenating agent, such as TiCl₄.

In an embodiment, the process includes pre-halogenating thebenzoate-containing magnesium chloride procatalyst precursor with ahalogenating agent prior to addition of the alkoxypropyl ester to thereaction mixture. The halogenating agent may be TiCl₄.

In an embodiment, the procatalyst composition is made by way of multiplecontact steps in accordance with one or more processes set forth incopending U.S. patent application Ser. No. 12/974,548 (attorney docketno. 70317) filed on Dec. 21, 2010, the entire content of which isincorporated by reference herein. The procatalyst composition withalkoxypropyl ester contains greater than 6.5 wt %, or greater than 10 wt% to 15 wt % alkoxypropyl ester. Weight percent is based on the totalweight of the procatalyst composition.

Applicant has surprisingly discovered that the procatalyst compositionwith the alkoxypropyl ester unexpectedly produces a procatalystcomposition with improved selectivity when compared to conventionalalkoxyalkyl ester-containing procatalysts. The present procatalystcomposition, with greater than 6.5 wt % alkoxypropyl ester,advantageously contains more alkoxyalkyl ester (i.e. alkoxypropyl ester)than conventional alkoxyalkyl ester-containing procatalysts. The presentprocatalyst composition is phthalate-free yet exhibits the same, orimproved, selectivity and/or catalyst activity, hydrogen response,and/or polymer melting point when compared to phthalate-containingprocatalyst compositions. These improvements make the presentprocatalyst composition suitable for commercial polymer production.

In addition, the present procatalyst composition contains a lower amountof titanium chloride, which may translate into lower levels of residualmetal and/or residual halide in the formant polymer. The residual metaland/or residual halide are detrimental in many polymer end-useapplications, such as capacitor film, for example.

The alkoxypropyl ester has the structure (I) set forth below.

R, R₁, R₂, R₃, and R₄ are the same or different. R is selected from anunsubstituted aliphatic C₃-C₂₀ secondary alkyl group, a substitutedaliphatic C₃-C₂₀ secondary alkyl group, an unsubstituted C₂-C₂₀ alkenylgroup and a substituted C₂-C₂₀ alkenyl group. R₁ is selected from anunsubstituted C₁-C₂₀ primary alkyl group, a substituted C₁-C₂₀ primaryalkyl group, and a C₂-C₂₀ alkenyl group. Each of R₂-R₄ is selected fromhydrogen, an unsubstituted C₁-C₂₀ primary alkyl group, a substitutedC₁-C₂₀ primary alkyl group, a C₂-C₂₀ alkenyl group, and combinationsthereof.

In an embodiment, each of R and R₁-R₄ is selected from asubstituted/unsubstituted C₂-C₂₀ alkene group with the structure (II)below.

C(H)═C(R₁₁)(R₁₂)   (II)

R₁₁ and R₁₂ are the same or different. Each of R₁₁ and R₁₂ is selectedfrom hydrogen and a C₁-C₁₈ hydrocarbyl group.

As used herein, the term “hydrocarbyl” or “hydrocarbon” is a substituentcontaining only hydrogen and carbon atoms, including branched orunbranched, saturated or unsaturated, cyclic, polycyclic, fused, oracyclic species, and combinations thereof Nonlimiting examples ofhydrocarbyl groups include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-,cycloalkenyl-, cycloalkadienyl-, aryl-, alkylaryl-, and alkynyl-groups.

As used herein, the term “substituted hydrocarbyl” or “substitutedhydrocarbon” is a hydrocarbyl group that is substituted with one or morenonhydrocarbyl substituent groups. A nonlimiting example of anonhydrocarbyl substituent group is a heteroatom. As used herein, a“heteroatom” is an atom other than carbon or hydrogen. The heteroatomcan be a non-carbon atom from Groups IV, V, VI, and VII of the PeriodicTable. Nonlimiting examples of heteroatoms include: halogens (F Cl, Br,I), N, O, P, B, S, and Si. A substituted hydrocarbyl group also includesa halohydrocarbyl group and a silicon-containing hydrocarbyl group. Asused herein, the term “halohydrocarbyl” group is a hydrocarbyl groupthat is substituted with one or more halogen atoms.

In an embodiment, the alkoxypropyl ester is 3-methoxypropyl isobutyrate.

In an embodiment, the magnesium moiety is a magnesium chloride. Thetitanium moiety is a titanium chloride.

The resulting procatalyst composition has a titanium content of fromabout 1.0 wt %, or about 1.5 wt %, or about 2.0 wt %, to about 6.0 wt %,or about 5.5 wt %, or about 5.0 wt %. The weight ratio of titanium tomagnesium in the solid procatalyst composition is suitably between about1:3 and about 1:160, or between about 1:4 and about 1:50, or betweenabout 1:6 and 1:30. The alkoxypropyl ester may be present in theprocatalyst composition in a molar ratio of alkoxypropyl ester tomagnesium of from about 0.005:1 to about 1:1, or from about 0.01:1 toabout 0.4:1. Weight percent is based on the total weight of theprocatalyst composition.

The procatalyst composition may comprise two or more embodimentsdisclosed herein.

Catalyst Composition

The present disclosure provides a catalyst composition. In anembodiment, the catalyst composition includes a procatalyst compositioncontaining the greater than 6.5 wt % alkoxypropyl ester, a cocatalyst,and an external electron donor. The procatalyst composition may be anyof the foregoing procatalyst compositions containing structures (I)-(II)as disclosed above.

As used herein, a “cocatalyst” is a substance capable of converting theprocatalyst to an active polymerization catalyst. The cocatalyst mayinclude hydrides, alkyls, or aryls of aluminum, lithium, zinc, tin,cadmium, beryllium, magnesium, and combinations thereof. In anembodiment, the cocatalyst is a hydrocarbyl aluminum compoundrepresented by the formula R_(n)AlX_(3-n) wherein n=1, 2, or 3,. R is analkyl, and X is a halide or alkoxide. In an embodiment, the cocatalystis selected from trimethylaluminum, triethylaluminum,triisobutylaluminum, and tri-n-hexylaluminum.

Nonlimiting examples of suitable hydrocarbyl aluminum compounds are asfollows: methylaluminoxane, isobutylaluminoxane, diethylaluminumethoxide, diisobutylaluminum chloride, tetraethyldialuminoxane,tetraisobutyldialuminoxane, diethylaluminum chloride, ethylaluminumdichloride, methylaluminum dichloride, dimethylaluminum chloride,triisobutylaluminum, tri-n-hexylaluminum, diisobutylaluminum hydride,di-n-hexylaluminum hydride, isobutylaluminum dihydride, n-hexylaluminumdihydride, diisobutylhexylaluminum, isobutyldihexylaluminum,trimethylaluminum, triethylaluminum, tri-n-propylaluminum,triisopropylaluminum, tri-n-butylaluminum, tri-n-octylaluminum,tri-n-decylaluminum, tri-n-dodecylaluminum, diisobutylaluminum hydride,and di-n-hexylaluminum hydride.

In an embodiment, the cocatalyst is triethylaluminum. The molar ratio ofaluminum to titanium is from about 5:1 to about 500:1, or from about10:1 to about 200:1, or from about 15:1 to about 150:1, or from about20:1 to about 100:1. In another embodiment, the molar ratio of aluminumto titanium is about 45:1.

As used herein, an “external electron donor” (or “EED”) is a compoundadded independent of procatalyst formation and includes at least onefunctional group that is capable of donating a pair of electrons to ametal atom. Bounded by no particular theory, it is believed thatprovision of one or more external electron donors in the catalystcomposition affects the following properties of the formant polymer:level of tacticity (i.e., xylene soluble material), molecular weight(i.e., melt flow), molecular weight distribution (MWD), and/or meltingpoint.

In an embodiment, the EED is a silicon compound having the generalformula (III):

SiR_(m)(OR′)_(4-m)   (III)

wherein R independently each occurrence is hydrogen or a hydrocarbyl oran amino group, optionally substituted with one or more substituentscontaining one or more Group 14, 15, 16, or 17 heteroatoms. R containsup to 20 atoms not counting hydrogen and halogen. R′ is a C₁-C₂₀ alkylgroup, and m is 0, 1, 2, or 3. In an embodiment, R is C₁₋₂₀ linearalkyl, C₆₋₁₂ aryl, aralkyl or alkylaryl, C₃₋₁₂ cycloalkyl, C₃₋₁₂branched alkyl, or C₂₋₁₂ cyclic amino group, R′ is C₁₋₄ alkyl, and m is0, 1, or 2.

In an embodiment, the silicon compound is dicyclopentyldimethoxysilane(DCPDMS), methylcyclohexyldimethoxysilane (MChDMS), orn-propyltrimethoxysilane (NPTMS), and any combination thereof In anembodiment, the silicon compound is diisopropyldimethoxysilane,isopropylisobutyldimethoxysilane, diisobutyldimethoxysilane,t-butylisopropyldimethoxysilane, cyclopentylpyrrolidinodimethoxysilane,bis(pyrrolidino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane, diethylaminotriethoxysilane,and any combination thereof.

Mixed External Electron Donor

In an embodiment, the present catalyst composition includes a mixedexternal electron donor (M-EED). As used herein, a “mixed externalelectron donor” (“M-EED”) comprises at least two of the followingcomponents: (i) a first selectivity control agent (SCA1), (ii) a secondselectivity control agent (SCA2), and (iii) an activity limiting agent(ALA).

Nonlimiting examples of suitable compounds for the SCA1 and/or SCA2include silicon compounds, such as alkoxysilanes; ethers and polyethers,such as alkyl-, cycloalkyl-, aryl-, mixed alkyl/aryl-, mixedalkyl/cycloalkyl-, and/or mixed cycloalkyl/aryl-ethers and/orpolyethers; esters and polyesters, especially alkyl, cycloalkyl- and/oraryl-esters of monocarboxylic or dicarboxylic acids, such as aromaticmonocarboxylic- or dicarboxylic-acids; alkyl- or cycloalkyl-ether orthioether derivatives of such esters or polyesters, such as alkyl etherderivatives of alkyl esters or diesters of aromatic monocarboxylic ordicarboxylic acids; and Group 15 or 16 heteroatom-substitutedderivatives of all of the foregoing; and amine compounds, such ascyclic, aliphatic or aromatic amines, more especially piperidine, pyrrolor pyridine compounds; all of the foregoing SCA's containing from 2 to60 carbons total and from 1 to 20 carbons in any alkyl or alkylenegroup, 3 to 20 carbons in any cycloalkyl or cycloalkylene group, and 6to 20 carbons in any aryl or arylene group.

In an embodiment, SCA1 and/or SCA2 are/is a silane composition havingthe structure (III) as disclosed above.

In an embodiment, SCA1 is a dimethoxysilane. The dimethoxysilane mayinclude a dimethoxysilane having at least one secondary alkyl and/or asecondary amino group directly bonded to the silicon atom. Nonlimitingexamples of suitable dimethoxysilanes includedicyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane,diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane,diisobutyldimethoxysilane, t-butylisopropyldimethoxysilane,cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane, and any combination of theforegoing. In a further embodiment, SCA1 isdicyclopentyldimethoxysilane.

In an embodiment, the SCA2 is a silicon compound selected from adiethoxysilane, a triethoxysilane, a tetraethoxysilane, atrimethoxysilane, a dimethoxysilane containing two linear alkyl groups,a dimethoxysilane containing two alkenyl groups, a diether, adialkoxybenzene, and any combination thereof.

Nonlimiting examples of suitable silicon compounds for SCA2 includedimethyldimethoxysilane, vinylmethyldimethoxysilane,n-octylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane,methyldimethoxysilane, 3-chloropropylmethyldimethoxysilane,2-chloroethylmethyldimethoxysilane, allyldimethoxysilane,(3,3,3-trifluoropropyl)methyldimethoxysilane,n-propylmethyldimethoxysilane, chloromethylmethyldimethoxysilane,di-n-octyldimethoxysilane, vinyl(chloromethyl)dimethoxysilane,methylcyclohexyldiethoxysilane, vinylmethyldiethoxysilane,1-(triethoxysilyl)-2-(diethoxymethylsilyl)ethane,n-octylmethyldiethoxysilane, octaethoxy-1,3,5-trisilapentane,n-octadecylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane,2-hydroxy-4-(3-methyldiethoxysilylpropoxy)diphenylketone,(3-glycidoxypropyl)methyldiethoxysilane, dodecylmethyldiethoxysilane,dimethyldiethoxysilane, diethyldiethoxysilane,1,1-diethoxy-1-silacyclopent-3-ene, chloromethylmethyldiethoxysilane,bis(methyldiethoxysilylpropyl)amine, 3-aminopropylmethyldiethoxysilane,(methacryloxymethyl)methyldiethoxysilane,1,2-bis(methyldiethoxysilyl)ethane, and diisobutyldiethoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane, benzyltriethoxysilane,butenyltriethoxysilane, (triethoxysilyl)cyclohexane,O-(vinyloxybutyl)-N-triethoxysilylpropylcarbamate,10-undecenyltrimethoxysilane, n-(3-trimethoxysilylpropyl)pyrrole,N-[5-(trimethoxysilyl)-2-aza-1-oxopentyl]caprolactam,(3,3,3-trifluoropropyl)trimethoxysilane, triethoxysilylundecanalethylene glycol acetal, (S)—N-triethoxysilylpropyl-O-menthocarbamate,triethoxysilylpropylethylcarbamate,N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole,(3-triethoxysilylpropyl)-t-butylcarbamate, styrylethyltrimethoxysilane,2-(4-pyridylethyl)triethoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane,(S)—N-1-phenylethyl-N′-triethoxysilylpropylurea,(R)—N-1-phenylethyl-N′-triethoxysilylpropylurea,N-phenylaminopropyltrimethoxysilane, N-phenylaminomethyltriethoxysilane,phenethyltrimethoxysilane, pentyltriethoxysilane,n-octyltrimethoxysilane, n-octyltriethoxysilane,7-octenyltrimethoxysilane, S-(octanoyl)mercaptopropyltriethoxysilane,n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane,methyltrimethoxysilane, methyltriethoxysilane,N-methylaminopropyltrimethoxysilane, 3-methoxypropyltrimethoxysilane,methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane,methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane,and O-(methacryloxyethyl)-N-(triethoxysilylpropyl)carbamate,tetramethoxysilane and/or tetraethoxysilane.

In an embodiment, SCA2 may be methylcyclohexyldiethoxysilane,di-isobutyldiethoxysilane, n-propyltriethoxysilane, tetraethoxysilane,din-butyl-dimethoxysilane, benzyltriethoxysilane,but-3-enyltriethoxysilane, 1-(triethoxysilyl)-2-pentene,(triethoxysilyl)cyclohexane, and any combination of the foregoing.

In an embodiment, the SCA2 is selected from a dimethoxysilane containingtwo linear alkyl groups, a dimethoxysilane containing two alkenyl groupsor hydrogen, wherein one or more hydrogen atoms may be substituted by ahalogen, and any combination thereof.

In an embodiment, SCA2 may be a diether, a dimer of a diether, adialkoxybenzene, a dimmer of a dialkoxybenzene, a dialkoxybenzene linkedby a linear hydrocarbon group, and any combination thereof It is notedthat the diethers for the ALA set forth below apply equally asnonlimiting examples for the SCA2 diether.

The M-EED may include an activity limiting agent (ALA). An “activitylimiting agent,” as used herein is a material that reduces catalystactivity at elevated temperature, namely, in a polymerization reactor atpolymerization conditions at a temperature greater than about 100° C.Provision of the ALA results in a self-limiting catalyst composition. Asused herein, a “self-limiting” catalyst composition is a catalystcomposition that demonstrates decreased activity at a temperaturegreater than about 100° C. In other words, “self-limiting” is thesignificant decline of catalyst activity when the reaction temperaturerises above 100° C. compared to the catalyst activity under normalpolymerization conditions with reaction temperature usually below 80° C.In addition, as a practical standard, if a polymerization process, suchas a fluidized bed, gas-phase polymerization running at normalprocessing conditions is capable of interruption and resulting collapseof the bed with reduced risk with respect to agglomeration of polymerparticles, the catalyst composition is said to be “self-limiting.”

The ALA may be an aromatic ester or a derivative thereof, an aliphaticester or derivative thereof, a diether, a poly(alkylene glycol) ester,and combinations thereof. Nonlimiting examples of suitable aromaticesters include C₁₋₁₀ alkyl or cycloalkyl esters of aromaticmonocarboxylic acids. Suitable substituted derivatives thereof includecompounds substituted both on the aromatic ring(s) or the ester groupwith one or more substituents containing one or more Group 14, 15 or 16heteroatoms, especially oxygen. Examples of such substituents include(poly)alkylether, cycloalkylether, arylether, aralkylether,alkylthioether, arylthioether, dialkylamine, diarylamine,diaralkylamine, and trialkylsilane groups. The aromatic carboxylic acidester may be a C₁₋₂₀ hydrocarbyl ester of benzoic acid wherein thehydrocarbyl group is unsubstituted or substituted with one or more Group14, 15 or 16 heteroatom containing substituents and C₁₋₂₀(poly)hydrocarbyl ether derivatives thereof, or C₁₋₄ alkyl benzoates andC₁₋₄ ring alkylated derivatives thereof, or methyl benzoate, ethylbenzoate, propyl benzoate, methyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-methoxybenzoate, and ethyl p-ethoxybenzoate.In an embodiment, the aromatic carboxylic acid ester is ethylp-ethoxybenzoate.

In an embodiment, the ALA is an aliphatic ester. The aliphatic ester maybe a C₄₋₃₀ aliphatic acid ester, may be a mono- or a poly- (two or more)ester, may be straight chain or branched, may be saturated orunsaturated, and any combination thereof The C₄₋₃₀ aliphatic acid estermay also be substituted with one or more Group 14, 15 or 16 heteroatomcontaining substituents. Nonlimiting examples of suitable C₄₋₃₀aliphatic acid esters include C₁₋₂₀ alkyl esters of aliphatic C₄₋₃₀monocarboxylic acids, C₁₋₂₀ alkyl esters of aliphatic C₈₋₂₀monocarboxylic acids, C₁₋₄ allyl mono- and diesters of aliphatic C₄₋₂₀monocarboxylic acids and dicarboxylic acids, C₁₋₄ alkyl esters ofaliphatic C₈₋₂₀ monocarboxylic acids and dicarboxylic acids, and C₄₋₂₀mono- or polycarboxylate derivatives of C₂₋₁₀₀ (poly)glycols or C₂₋₁₀₀(poly)glycol ethers. In a further embodiment, the C₄₋₃₀ aliphatic acidester may be isopropyl myristate and/or di-n-butyl sebacate.

In an embodiment, the ALA is isopropyl myristate.

In an embodiment, the ALA is a diether. The diether may be a dialkyldiether represented by the following formula,

wherein R₁ to R₄ are independently of one another an alkyl, aryl oraralkyl group having up to 20 carbon atoms, which may optionally containa group 14, 15, 16, or 17 heteroatom, provided that R₁ and R₂ may be ahydrogen atom. Nonlimiting examples of suitable dialkyl ether compoundsinclude dimethyl ether, diethyl ether, dibutyl ether, methyl ethylether, methyl butyl ether, methyl cyclohexyl ether,2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,2,2-di-n-butyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane,2-ethyl-2-n-butyl-1,3-dimethoxypropane,2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dimethyl-1,3-diethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2,2-dicyclopentyl-1,3-dimethoxypropane,2-n-propyl-2-cyclohexyl-1,3-diethoxypropane, and9,9-bis(methoxymethyl)fluorene. In a further embodiment, the dialkylether compound is 2,2-diisobutyl-1,3-dimethoxypropane.

In an embodiment, the ALA is a poly(alkylene glycol)ester. Nonlimitingexamples of suitable poly(alkylene glycol) esters include poly(alkyleneglycol) mono- or diacetates, poly(alkylene glycol) mono- ordi-myristates, poly(alkylene glycol) mono- or di-laurates, poly(alkyleneglycol) mono- or di-oleates, glyceryl tri(acetate), glyceryl tri-esterof C₂₋₄₀ aliphatic carboxylic acids, and any combination thereof. In anembodiment, the poly(alkylene glycol)moiety of the poly(alkylene glycol)ester is a polyethylene glycol).

In an embodiment, the molar ratio of aluminum to ALA may be 1.4-85:1, or2.0-50:1, or 4-30:1. For ALA that contains more than one carboxylategroup, all the carboxylate groups are considered effective components.For example, a sebacate molecule contains two carboxylate functionalgroups is considered to have two effective functional molecules.

In an embodiment, the M-EED comprises isopropyl myristate as the ALA,dicyclopentyldimethoxysilane as SCAT, and SCA2 is selected frommethylcyclohexyldiethoxysilane, diisobutyldiethoxysilane,di-n-butyl-dimethoxysilane, n-propyltriethoxysilane,benzyltriethoxysilane, but-3-enyltriethoxysilane,1-(triethoxysilyl)-2-pentene, (triethoxysilyl)cyclohexane,tetraethoxysilane, 1-ethoxy-2-(6-(2-ethoxyphenoxy)hexyloxy)benzene,1-ethoxy-2-n-pentoxybenzene, and any combination thereof.

In an embodiment, the M-EED includes dicyclopentyldimethoxysilane asSCA1, tetraethoxysilane as SCA2, and isopropyl myristate as the ALA.

In an embodiment, the M-EED includes dicyclopentyldimethoxysilane asSCA1, n-propyltriethoxysilane as SCA2, and isopropyl myristate as theALA.

The present catalyst composition may comprise two or more embodimentsdisclosed herein.

In an embodiment, a polymerization process is provided. Thepolymerization process includes contacting propylene and optionally atleast one other olefin with a catalyst composition in a polymerizationreactor under polymerization conditions. The catalyst composition may beany catalyst composition disclosed herein and includes a procatalystcomposition with the alkoxypropyl ester, a cocatalyst, an externalelectron donor, or a mixed external electron donor (M-EED). Theprocatalyst composition with the alkoxypropyl ester includes greaterthan 6.5 wt % of an alkoxypropyl ester. The process also includesforming a propylene-based polymer having a melt flow rate greater than 4g/10 min. The propylene-based polymer contains an alkoxypropyl ester.

In an embodiment, the catalyst composition may or may not include amixed external electron donor (M-EED) composed of an activity limitingagent (ALA), a first selectivity control agent (SCA1), and a secondselectivity control agent (SCA2). The process includes forming apropylene-based polymer containing an alkoxypropyl ester and having amelt flow rate greater than 4 g/10 min, or greater than 5 g/10 min, orgreater than 6 g/10 min, or greater than 10 g/10 min, or greater than 25g/10 min, or greater than 50 g/10 min, or greater than 75 g/10 min, orgreater than 100 g/10 min to 2000 g/10 min, or 1000 g/10 min, or 500g/10 min, or 400 g/10 min, or 200 g/10 min.

In an embodiment, the process produces a propylene-based polymer with aPDI from 3.5 to 6.0.

In an embodiment, the present catalyst composition includes a SCA/ALAmixture of: (i) a selectivity control agent selected from structure(III), SCA1, or SCA2 as disclosed above, and (ii) an activity limitingagent (ALA). Nonlimiting examples of suitable SCA/ALA mixtures includedicyclopentyldimethoxysilane and isopropyl myristate;dicyclopentyldimethoxysilane and poly(ethylene glycol)laurate;diisopropyldimethoxysilane and isopropyl myristate;methylcyclohexyldimethoxysilane and isopropyl myristate;methylcyclohexyldimethoxysilane and ethyl 4-ethoxybenzoate;n-propyltrimethoxysilane and isopropyl myristate; and combinationsthereof.

The process includes contacting propylene and optionally at least oneother olefin with the catalyst composition in a polymerization reactor.One or more olefin monomers can be introduced into the polymerizationreactor along with the propylene to react with the catalyst and to forma polymer, a copolymer, (or a fluidized bed of polymer particles).Nonlimiting examples of suitable olefin monomers include ethylene, C₄₋₂₀α-olefins, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,1-heptene, 1-octene, 1-decene, 1-dodecene and the like; C₄₋₂₀ diolefins,such as 1,3-butadiene, 1,3-pentadiene, norbornadiene,5-ethylidene-2-norbornene (ENB) and dicyclopentadiene; C₈₋₄₀ vinylaromatic compounds including styrene, o-, m-, and p-methylstyrene,divinylbenzene, vinylbiphenyl, vinylnapthalene; and halogen-substitutedC₈₋₄₀ vinyl aromatic compounds such as chlorostyrene and fluorostyrene.

In an embodiment, the process includes contacting propylene with thecatalyst composition to form a propylene homopolymer.

In an embodiment, the process includes introducing an activepropylene-based polymer from a first polymerization reactor into asecond polymerization reactor. The first polymerization reactor and thesecond polymerization reactor operate in series, whereby the effluentfrom the first polymerization reactor is charged to the secondpolymerization reactor and one or more additional (or different) olefinmonomer(s) is/are added to the second polymerization reactor to continuepolymerization to form a propylene copolymer or a propylene impactcopolymer. In a further embodiment, each of the first polymerizationreactor and the second polymerization reactor is a gas phasepolymerization reactor.

As used herein, “polymerization conditions” are temperature and pressureparameters within a polymerization reactor suitable for promotingpolymerization between the catalyst composition and an olefin to formthe desired polymer. The polymerization process may be a gas phase, aslurry, or a bulk polymerization process, operating in one, or more thanone, polymerization reactor. Accordingly, the polymerization reactor maybe a gas phase polymerization reactor, a liquid-phase polymerizationreactor, or a combination thereof.

It is understood that provision of hydrogen in the polymerizationreactor is a component of the polymerization conditions. Duringpolymerization, hydrogen is a chain transfer agent and affects themolecular weight (and correspondingly the melt flow rate) of theresultant polymer.

In an embodiment, polymerization occurs by way of liquid phasepolymerization.

In an embodiment, polymerization occurs by way of gas phasepolymerization. As used herein, “gas phase polymerization” is thepassage of an ascending fluidizing medium, the fluidizing mediumcontaining one or more monomers, in the presence of a catalyst through afluidized bed of polymer particles maintained in a fluidized state bythe fluidizing medium. “Fluidization,” “fluidized,” or “fluidizing” is agas-solid contacting process in which a bed of finely divided polymerparticles is lifted and agitated by a rising stream of gas. Fluidizationoccurs in a bed of particulates when an upward flow of fluid through theinterstices of the bed of particles attains a pressure differential andfrictional resistance increment exceeding particulate weight. Thus, a“fluidized bed” is a plurality of polymer particles suspended in afluidized state by a stream of a fluidizing medium. A “fluidizingmedium” is one or more olefin gases, optionally a carrier gas (such asH₂ or N₂) and optionally a liquid (such as a hydrocarbon) which ascendsthrough the gas-phase reactor.

A typical gas-phase polymerization reactor (or gas phase reactor)includes a vessel (i.e., the reactor), the fluidized bed, a distributionplate, inlet and outlet piping, a compressor, a cycle gas cooler or heatexchanger, and a product discharge system. The vessel includes areaction zone and a velocity reduction zone, each of which is locatedabove the distribution plate. The bed is located in the reaction zone.In an embodiment, the fluidizing medium includes propylene gas and atleast one other gas such as an olefin and/or a carrier gas such ashydrogen or nitrogen.

In an embodiment, the contacting occurs by way of feeding the catalystcomposition into the polymerization reactor and introducing the olefininto the polymerization reactor. In an embodiment, the process includescontacting the olefin with a cocatalyst. The cocatalyst can be mixedwith the procatalyst composition (pre-mix) prior to the introduction ofthe procatalyst composition into the polymerization reactor. In anotherembodiment, cocatalyst is added to the polymerization reactorindependently of the procatalyst composition. The independentintroduction of the cocatalyst into the polymerization reactor can occursimultaneously, or substantially simultaneously, with the procatalystcomposition feed.

Applicants have surprisingly and unexpectedly discovered that thepresence of the mixed external electron donor provides a catalystcomposition that is self-limiting and produces propylene-based polymerswith high stiffness and high melt flow in a single polymerizationreactor under standard polymerization conditions. Not wishing to bebound by any particular theory, it is believed that the ALA improvesoperability in the polymerization reactor by preventing a run-awayreaction, polymer sheeting, and/or polymer agglomeration caused byexcessive heat. Provision of SCA1 and SCA2 enables the formation of ahigh stiffness (i.e., T_(MF) greater than about 170° C.) and high MFRpropylene-based polymer with utilization of standard hydrogen levels.

The present disclosure provides a polymeric composition. The polymericcomposition may be made by any of the foregoing polymerizationprocesses. In an embodiment, a polymeric composition is provided andincludes a propylene-based polymer containing an alkoxypropyl ester. Thepropylene-based polymer has a melt flow rate greater than 4 g/10 min, orgreater than 5 g/10 min, or greater than 6 g/10 min, or greater than 10g/10 min, or greater than 25 g/10 min, or greater than 50 g/10 min, orgreater than 75 g/10 min, or greater than 100 g/10 min to 2000 g/10 min,or 1000 g/10 min, or 500 g/10 min, or 400 g/10 min, or 200 g/10 min.

In an embodiment, the polymeric composition has a melt flow rate greaterthan 100 g/10 min.

In an embodiment, the propylene-based polymer has a PDI from 3.5 to 6.0.

In an embodiment, the polymeric composition is a propylene homopolymer.

In an embodiment, the polymeric composition is a propylene copolymer(such as a propylene/ethylene copolymer).

The present polymerization process may comprise two or more embodimentsdisclosed herein.

Definitions

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical (or hydrocarbylgroup). Nonlimiting examples of suitable alkyl radicals include, forexample, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl(or 2-methylpropyl), etc. The alkyls have 1 and 20 carbon atoms.

The term “aryl,” as used herein, refers to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. The aryls have 1 and20 carbon atoms.

The terms “blend” or “polymer blend,” as used herein, is a blend of twoor more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized ethylene monomer(based on the total weight of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, usually employed torefer to polymers prepared from two different monomers, and polymersprepared from more than two different types of monomers.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike.

A “primary alkyl group” has the structure —CH₂R₁ wherein R₁ is hydrogenor a substituted/unsubstituted hydrocarbyl group.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

A “secondary alkyl group” has the structure —CHR₁R₂ wherein each of R₁and R₂ is a substituted/unsubstituted hydrocarbyl group.

The term “substituted alkyl,” as used herein, refers to an alkyl as justdescribed in which one or more hydrogen atom bound to any carbon of thealkyl is replaced by another group such as a halogen, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, haloalkyl, hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

A “tertiary alkyl group” has the structure —CR₁R₂R₃ wherein each of R₁,R₂, and R₃ is a substituted/unsubstituted hydrocarbyl group.

Test Methods

Final melting point T_(MF) is the temperature to melt the most perfectcrystal in the sample and is regarded as a measure for isotacticity andinherent polymer crystallizability. The test was conducted using a TAQ100 Differential Scanning Calorimeter. A sample is heated from 0° C. to240° C. at a rate of 80° C./min, cooled at the same rate to 0° C., thenheated again at the same rate up to 150° C., held at 150° C. for 5minutes and the heated from 150° C. to 180° C. at 1.25° C/min. TheT_(MF) is determined from this last cycle by calculating the onset ofthe baseline at the end of the heating curve.

Testing procedure:

-   -   (1) Calibrate instrument with high purity indium as standard.    -   (2) Purge the instrument head/cell with a constant 50 ml/min        flow rate of nitrogen constantly.    -   (3) Sample preparation:        -   Compression mold 1.5 g of powder sample using a            30-G302H-18-CX Wabash Compression Molder (30 ton): (a) heat            mixture at 230° C. for 2 minutes at contact; (b) compress            the sample at the same temperature with 20 ton pressure for            1 minute; (c) cool the sample to 45° F. and hold for 2            minutes with 20 ton pressure; (d) cut the plaque into 4 of            about the same size, stack them together, and repeat steps            (a)-(c) in order to homogenize sample.    -   (4) Weigh a piece of sample (preferably between 5 to 8 mg) from        the sample plaque and seal it in a standard aluminum sample pan.        Place the sealed pan containing the sample on the sample side of        the instrument head/cell and place an empty sealed pan in the        reference side. If using the auto sampler, weigh out several        different sample specimens and set up the machine for a        sequence.    -   (5) Measurements:        -   (i) Data storage: off        -   (ii) Ramp 80.00° C./min to 240.00° C.        -   (iii) Isothermal for 1.00 min        -   (iv) Ramp 80.00° C./min to 0.00° C.        -   (v) Isothermal for 1.00 min        -   (vi) Ramp 80.00° C./min to 150.00° C.        -   (vii) Isothermal for 5.00 min        -   (viii) Data storage: on        -   (ix) Ramp 1.25° C./min to 180.00° C.        -   (x) End of method    -   (6) Calculation: T_(MF) is determined by the interception of two        lines. Draw one line from the base-line of high temperature.        Draw another line from through the deflection of the curve close        to the end of the curve at high temperature side.

Melt flow rate (MFR) is measured in accordance with ASTM D 1238-01 testmethod at 230° C. with a 2.16 kg weight for propylene-based polymers.

Polydispersity Index (PDI) is measured by an AR-G2 rheometer which is astress control dynamic spectrometer manufactured by TA Instruments usinga method according to Zeichner G R, Patel P D (1981) “A comprehensiveStudy of Polypropylene Melt Rheology” Proc. Of the 2nd World Congress ofChemical Eng., Montreal, Canada. An ETC oven is used to control thetemperature at 180° C.±0.1° C. Nitrogen is used to purge the inside theoven to keep the sample from degradation by oxygen and moisture. A pairof 25 mm in diameter cone and plate sample holder is used. Samples arecompress molded into 50 mm×100 mm×2 mm plaque. Samples are then cut into19 mm square and loaded on the center of the bottom plate. Thegeometries of upper cone is (1) Cone angle: 5:42:20 (deg:min:I); (2)Diameter: 25 mm; (3) Truncation gap: 149 micron. The geometry of thebottom plate is 25 mm cylinder.

Testing Procedure:

-   -   (1) The cone & plate sample holder are heated in the ETC oven at        180° C. for 2 hours. Then the gap is zeroed under blanket of        nitrogen gas.    -   (2) Cone is raised to 2.5 mm and sample loaded unto the top of        the bottom plate.    -   (3) Start timing for 2 minutes.    -   (4) The upper cone is immediately lowered to slightly rest on        top of the sample by observing the normal force.    -   (5) After two minutes the sample is squeezed down to 165 micron        gap by lower the upper cone.    -   (6) The normal force is observed. When the normal force is down        to <0.05 Newton the excess sample is removed from the edge of        the cone and plate sample holder by a spatula.    -   (7) The upper cone is lowered again to the truncation gap which        is 149 micron.    -   (8) An Oscillatory Frequency Sweep test is performed under these        conditions:        -   Test delayed at 180° C. for 5 minutes.        -   Frequencies: 628.3r/s to 0.1r/s.        -   Data acquisition rate: 5 point/decade.        -   Strain: 10%    -   (9) When the test is completed the crossover modulus (Gc) is        detected by the Rheology Advantage Data Analysis program        furnished by TA Instruments.    -   (10)PDI=100,000÷Gc (in Pa units).

Xylene Solubles (XS) is measured using a ¹H NMR method as described inU.S. Pat. No.5,539,309, the entire content of which is incorporatedherein by reference.

By way of example and not by limitation, examples of the presentdisclosure will now be provided.

EXAMPLES

1. Procatalyst Precursor

MagTi-1 is used as a procatalyst precursor. MagTi-1 is a mixed Mg/Tiprecursor with composition of Mg₃Ti(OEt)₈Cl₂ (prepared according toexample 1 in U.S. Pat. No. 6,825,146).

SHAC™ 310 is used as a procatalyst precursor. SHAC™ 310 is abenzoate-containing catalyst with ethyl benzoate as the internalelectron donor made according to Example 2 in U.S. Pat. No. 6,825,146.Titanium content for each of the resultant procatalyst compositions islisted in Table 1. The peaks for internal donors are assigned accordingto retention time from GC analysis.

A. First Contact

3.00 g of MagTi-1 (or 2.0 g SHAC™ 310) is charged into a flask equippedwith mechanical stirring and with bottom filtration. 60 ml of a mixedsolvent of TiCl₄ and chlorobenzene (1/1 by volume) is introduced intothe flask followed immediately by addition of 2.52 mmol of alkoxypropylester. The mixture is heated to 115° C. in 15 minutes and remains at115° C. for 60 minutes with stirring at 250 rpm before filtering off theliquid.

B. Second Contact/Halogenation

60 ml of mixed solvent and optionally 2.52 mmol of alkoxypropyl esterare added again and the reaction is allowed to continue at the samedesired temperature for 30 minutes with stirring followed by filtration.

C. Third Contact/Halogenation

Same as second halogenation.

The final procatalyst composition is rinsed three times at roomtemperature with 70 ml of isooctane and dried under nitrogen flow for 2hours.

Procatalyst properties are set forth in Table 1 below. Weight percent isbased on total weight of the procatalyst composition. Abbreviations inTable 1 indicate the following: AE—Alkoxypropyl ester, EtO—Ethoxide.

TABLE 1 Ref Procatalyst Ti OEt AE Procatalyst # Structure Name Precursor(%) (%) (%) Number 30

3-methoxy-2- methoxypropyl benzoate MagTi SHAC ™ 310 2.60 2.32 0.42 0.27 8.42 10.94 C-30-1* C-30-S* 37

3-methoxypropyl isobutyrate MagTi SHAC ™ 310 3.40 2.44 0.30 0.34  2.70 6.77 C-37-1* C-37-S 38

3-methoxypropyl 3- methylbutanoate MagTi SHAC ™ 310 2.93 1.97 0.68 0.29 3.58  8.16 C-38-1* C-38-S* 39

3-methoxypropyl pivalate MagTi SHAC ™ 310 2.72 2.67 0.31 0.24  6.1019.22 C-91-1* C-39-S* 41

(9-(methoxymethyl)- 9H-fluoren 9- yl)methyl pivalate MagTi SHAC ™ 3104.86 3.09 0.52 0.25 NM NM C-40-1* C-40-S* *= Comparative

2. Polymerization

Polymerization is performed in liquid propylene in a 1-gallon autoclave.After conditioning, the reactor is charged with 1375 g of propylene anda targeted amount of hydrogen and brought to 62° C. 0.25 mmol ofdicyclopentyldimethoxysilane (DCPDMS) is added to a 0.27 Mtriethylaluminum solution in isooctane, followed by addition of a 5.0 wt% procatalyst slurry in mineral oil (actual solid weight is indicated inTable 2 below). The mixture is premixed at ambient temperature for 20minutes before being injected into the reactor to initiate thepolymerization. The premixed catalyst components are flushed into thereactor with isooctane using a high pressure catalyst injection pump.After the exotherm, the temperature is maintained at 67° C. Totalpolymerization time was 1 hour.

Polymer samples are tested for melt flow rate (MFR), xylene solubles(XS), polydispersity index (PDI), and final melting point (T_(MF)). XSis measured using ¹H NMR method.

Catalyst performance and polymer properties are provided in Table 2below.

-   -   NM=Not measured    -   N/A=Not available

TABLE 2 Pro- Procatalyst Procatalyst catalyst Al/ H₂ MFR XS Activity Ref# Precursor Number (mg) SCA (mmol) (g/10 min) (%) (kg/g-hr) 30 MagTiC-30-1* 16.7 6.84 83.5 4.4 7.74 11.4 SHAC ™ C-30-S* 16.7 6.84 83.5 4.95.01 9.6 310 37 MagTi C-37-1* 16.7 6.84 67.0 4.9 8.92 11.7 SHAC ™ C-37-S16.7 6.84 67.0 10.5 3.76 19.3 310 38 MagTi C-38-1* 16.7 6.84 67.0 6.59.75 7.8 SHAC ™ C-38-S* 16.7 6.84 44.6 4.1 7.38 6.3 310 39 MagTi C-91-1*16.7 6.84 44.6 6.1 7.79 12.1 SHAC ™ C-39-S* 16.7 6.84 44.6 4.9 6.27 11.0310 41 MagTi C-40-1* 16.7 6.84 67.0 8.2 8.85 22.7 SHAC ™ C-40-S* 16.76.84 67.0 9.1 8.57 22.3 310 *= Comparative

Data from Table 2 shows that low XS and good catalyst activity areobtained using a procatalyst containing an alkoxypropyl ester with asecondary alkyl group attached to the carboxylate group (IED 37) on aSHAC™ 310 precursor. High XS is observed for IED's when the groupattached to the carboxylate moiety is a phenyl group (IED 30), a primaryalkyl group (IED 38), and a tertiary alkyl group (IED 39). The XSbecomes very high when the substituents at the C₃-linker are bulky (IED41). In addition, XS is also higher when MagTi is used as procatalystprecursor.

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

1. The process of claim 6 wherein the alkoxypropyl ester has thestructure (I)

wherein R, R₁, R₂, R₃, and R₄ are the same or different, R is selectedfrom the group consisting of an unsubstituted aliphatic C₃-C₂₀ secondaryalkyl group, a substituted aliphatic C₃-C₂₀ secondary alkyl group, anunsubstituted C₂-C₂₀ alkenyl group, and a substituted C₂-C₂₀ alkenylgroup; R₁ is selected from the group consisting of an unsubstitutedC₁-C₂₀ primary alkyl group, a substituted C₁-C₂₀ primary alkyl group,and a C₂-C₂₀ alkenyl group; each of R₂-R₄ is selected from the groupconsisting of hydrogen, a C₁-C₂₀ primary alkyl group, a substitutedC₁-C₂₀ primary alkyl group, a C₂-C₂₀ alkenyl group, and combinationsthereof.
 2. The process of claim 1 wherein at least one of R₂-R₄ ishydrogen.
 3. The process of claim 1 wherein at least two of R₂-R₄ arehydrogen.
 4. The process of claim 1 wherein any of R, R₁, R₂ R₃ and R₄is a C₂-C₂₀ alkene group with the structure (II)C(H)═C(R₁₁)(R₁₂)   (II) wherein R₁₁ and R₁₂ are the same or different,each of R₁₁ and R₁₂ is selected from the group consisting of hydrogenand a C₁-C₁₈ hydrocarbyl group.
 5. The process of claim 1 wherein theprocatalyst composition comprises greater than 10 wt % of thealkoxypropyl ester.
 6. A process comprising: contacting a procatalystprecursor with a halogenating agent in the presence of an alkoxypropylester, the procatalyst precursor comprising a benzoate-containingmagnesium chloride; and forming a procatalyst composition comprising amagnesium moiety, a titanium moiety, and an internal electron donorcomprising the alkoxypropyl ester.
 7. The process of claim 6 comprisingpre-halogenating the procatalyst precursor with the halogenating agentbefore the contacting.
 8. The process of claim 6 comprising forming aprocatalyst composition comprising greater than 6.5 wt % alkoxypropylester.
 9. A polymerization process comprising: contacting, underpolymerization conditions, propylene and optionally one or morecomonomers with a catalyst composition comprising the procatalystcomposition of claim 8, a cocatalyst, and an external electron donor;and forming a propylene-based polymer.
 10. The process of claim 9comprising forming a propylene-based polymer having a melt flow rategreater than 4 g/10 min.
 11. The process of claim 9 comprising: forminga propylene-based polymer comprising an alkoxypropyl ester and having amelt flow rate greater than 4 g/10 min.
 12. The process of claim 9comprising forming a propylene-based polymer having a polydispersityindex from 3.5 to 6.0.
 13. The process of claim 9 wherein theprocatalyst composition comprises 3-methoxypropyl isobutyrate, theprocess comprising forming a propylene-based polymer comprising3-methoxypropyl isobutyrate.